Process for Obtaining Catalyst Composites MeAPO and Their Use in Conversion of Organics to Olefins

ABSTRACT

A mixture can include 0.01 to 30 weight % of a medium or large pore crystalline silicoaluminate, silicoaluminophosphate materials, or silicoaluminate mesoporous molecular sieves (A), and 99.99 to 70 weight % of a MeAPO molecular sieve. The mixture can be included in a catalyst. An XTO process can include contacting an oxygen-containing, halogenide-containing, or sulphur-containing organic feedstock with the catalyst under conditions effective to convert the organic feedstock to olefin products. A combined XTO and OCP process can include contacting the organic feedstock with the catalyst at conditions effective to convert at least a portion of the organic feedstock to form an XTO reactor effluent including light olefins and a heavy hydrocarbon fraction, separating the light olefins from the heavy hydrocarbon fraction, and contacting the heavy hydrocarbon fraction in an OCP reactor at conditions effective to convert at least a portion of the heavy hydrocarbon fraction to light olefins.

FIELD OF THE INVENTION

The present invention relates to catalyst composites comprisingpromoters and mixtures of molecular sieves containing MeAPO, as well astheir use in conversion of organics to olefins. More precisely themixture of molecular sieves comprises MeAPO and a crystallinesilicoaluminate or silicate molecular sieve. The crystallinesilicoaluminate or silicate molecular sieves have medium to large poresizes in comparison with the small pore sizes of the MeAPO. The mixturestogether with the promoter of the invention provide useful catalystcomposites suitable for a variety of processes including cracking,hydrocracking, isomerization, reforming, dewaxing, alkylation,transalkylation and conversion of oxygenates (or halogenide-containingor sulphur-containing organic compounds) to light olefins.

BACKGROUND OF THE INVENTION

The limited supply and increasing cost of crude oil has prompted thesearch for alternative processes for producing hydrocarbon products. Onesuch process is the conversion of oxygen-containing (by way of examplemethanol), halogenide-containing or sulphur-containing organic compoundsto hydrocarbons and especially light olefins (by light olefins it ismeant C₂ to C₄ olefins) or gasoline and aromatics. In the presentapplication the conversion of said oxygen-containing (also referred toas oxygenates), halogenide-containing or sulphur-containing organiccompounds to hydrocarbons and especially light olefins is referred to asthe XTO process. The interest in the XTO process is based on the factthat feedstocks, especially methanol can be obtained from coal, biomass,organic waste or natural gas by the production of synthesis gas which isthen processed to produce methanol. The XTO process can be combined withan OCP (olefins cracking process) process to increase production ofolefins. The XTO process produces light olefins such as ethylene andpropylene as well as heavy hydrocarbons such as butenes and above. Theseheavy hydrocarbons are cracked in an OCP process to give mainly ethyleneand propylene.

U.S. Pat. No. 6,951,830B2 relates to a catalyst composition, a method ofmaking the same and its use in the conversion of a feedstock, preferablyan oxygenated feedstock, into one or more olefin(s), preferably ethyleneand/or propylene. The catalyst composition comprises a molecular sieve,such as a silicoaluminophosphate and/or an aluminophosphate,hydrotalcite, and optionally a rare earth metal component. The rareearth metal compound can be in the form of acetates, halides, oxides,oxyhalides, hydroxides, sulphides, sulphonates, borides, borates,carbonates, nitrates, carboxylates and mixtures thereof.

US20070043250A1 describes an oxygenate conversion catalyst useful in theconversion of oxygenates such as methanol to olefinic products which isimproved by the use of a catalyst combination based on a molecular sievein combination with a co-catalyst comprising a mixed metal oxidecomposition which has oxidation/reduction functionality under theconditions of the conversion. This metal oxide co-catalyst componentwill comprise a mixed oxide of one or more, preferably at least two,transition metals, usually of Series 4, 5 or 6 of the Periodic Table,with the metals of Series 4 being preferred, as an essential componentof the mixed oxide composition. The preferred transition metals arethose of Groups 5, especially titanium and vanadium, Group 6, especiallychromium or molybdenum, Group 7, especially manganese and Group 8,especially cobalt or nickel. Other metal oxides may also be present. Thepreferred molecular sieve components in these catalysts are the highsilica zeolites and the silicoaluminaphosphates (SAPOs), especially thesmall pore SAPOs (8-membered rings), such as SAPO-34. These catalystcombinations exhibiting reduced coke selectivity have the potential ofachieving extended catalyst life. In addition, these catalysts have thecapability of selectively converting the hydrogen produced during theconversion to liquid products, mainly water, reducing the demand onreactor volume and product handling.

U.S. Pat. No. 7,186,875 discloses a process for converting anoxygenate-containing feedstock into one or more olefins in a reactorsystem including a plurality of fixed bed reactors each containing acatalyst composition comprising a molecular sieve and at least one metaloxide having an uptake of carbon dioxide at 100° C. of at least 0.03mg/m² of the metal oxide. Each reactor is sequentially rotated betweenat least one operating mode, wherein the catalyst composition in thereactor is contacted with the oxygenate-containing feedstock, and aregeneration mode, wherein the catalyst composition in the reactor iscontacted with a regeneration medium. The molecular sieve is asilicoaluminophosphate (SAPO) and/or a metal substituted SAPO. The metaloxide used in the composition, it is stated, is different from typicallyused binders and/or matrix material, in that it extends the life of thecatalyst composition. Suitable metal oxides include those metal oxideshaving a Group 2, Group 3 (including the Lanthanides and Actinides) orGroup 4 metal. There is no mention of any metal salts.

US 2003/0176752 describes a catalyst composition, a method making thesame and its use in the conversion of a feedstock, preferably anoxygenated feedstock, into one or more olefin(s), preferably ethyleneand/or propylene. The catalyst composition comprises a molecular sieveand at least one oxide of a metal from Group 4, optionally incombination with at least one metal from Groups 2 and 3. The metal oxidehas an uptake of carbon dioxide at 100° C. of at least 0.03 mg/m³. Themolecular sieve is preferably a silicoaluminophosphate and/or metalderivatives thereof.

US 2004/0030213 discloses describes an oxygenate conversion catalystbased a combination of a molecular sieve such as SAPO-34 and an oxide ofa metal of Group 3, including the lanthanide series and the actinideseries. Examples of such oxides include lanthanum oxide, yttrium oxide,scandium oxide, cerium oxide, praseodymium oxide, neodymium oxide,samarium oxide and thorium oxide.

This catalytic combination is reported to result in similar advantageswhen used in methanol conversion reactions and, in addition, results ina reduction in the amounts of undesirable by-products such as aldehydesand ketones, especially acetaldehyde. In addition, it is claimed thatthe catalyst compositions are less susceptible to coke formation andthus have longer lifetimes. It is also stated that the higher density ofthese catalyst compositions is believed to improve operability in theoverall conversion process. The denser catalyst particles are retainedto a greater extent within the unit, whether in the reactor or itsassociated regenerator, resulting in lower catalyst losses.

WO 1998029370 discloses the conversion of oxygenates to olefins over asmall pore (less than 5 nm) non-zeolitic molecular sieve containing anoxide of a lanthanide metal or an actinide metal, scandium, yttrium, aGroup 4 metal, a Group 5 metal or combinations thereof. Themetal-containing compound is introduced to the non-zeolitic molecularsieve in the form of the corresponding halide, sulphate, acetate,formate, propionate, oxalate, maleate, fumarate, carboxylate, alkoxide,carbonyl, nitrate or mixtures thereof. These small pore molecular sievecompositions are claimed to be more stable even at high conversionrates. These salts however are oxide-precursor salts and thus not stableat the high temperature conditions of the MTO process. Furthermore,selectivity to propylene is markedly low.

Molecular sieves in combination with matrix and binder components forXTO processes are known in the art. Usually, the binder and matrix arechemically neutral materials, typically serving only to provide desiredphysical characteristics to the catalyst composition. Usually, they havevery little effect on catalytic performance. These molecular sievecatalyst compositions are formed by combining the molecular sieve andthe matrix e.g. an inorganic oxide such as alumina, titania, zirconia,silica or silica-alumina with a binder, e.g. clay, to form a cohesive,mechanically stable, attrition-resistant composite of the sieve, matrixmaterial and binder. In particular, the use of silica (SiO₂) as abinder/matrix material is well known in the art. This solid is neutraland is selected when catalytic effects of the binder/matrix areundesired. Typically, rare earth elements, which are very expensive, areused in such catalyst composites.

Metal is introduced typically in the form of oxides/oxide-precursorsalts by ion-exchange or impregnation. However,ion-exchange/impregnation potentially leads to the modification of theacidity of catalytic sites throughout the whole microporous structure ofthe molecular sieve. This could lead to decreased catalytic activity.Metal oxides are chemically active compounds. Without taking specialprecautions during pre-treatment and catalyst formulation thesecompounds may partially damage the molecular sieve pore structure. Theproposed present invention is very different from the prior art. Itavoids the use of metal oxides or unstable oxide-precursor salts. Thecombination of molecular sieves with chemically inert metal salts whichare stable under the conversion process of the oxygenates to theolefins, allows selectively modifying only the sites located on theexternal surface and in the pore mouths of the molecular sieve. As aresult, the formation of side products is minimised and coke formationis decreased without losses in the catalyst's activity.

Small pore silicoaluminophosphate (SAPO) molecular sieve catalysts haveexcellent selectivity in oxygenates to light olefin reactions. However,these catalysts have a tendency to deactivate rapidly during theconversion of oxygenates to olefins and the ratio C3/C2 could beimproved. Therefore a need exists for methods to decrease the rate ofdeactivation of small pore molecular sieve catalysts during suchconversions and to improve the yield of light olefins and the C3/C2ratio.

It has been discovered that addition of a small amount of metal salts toa small pore MeAPO molecular sieve or optionally to a compositemolecular sieve containing a combination of small pore MeAPO molecularsieve with medium or large pore crystalline silicoaluminate,silicoaluminophosphate materials or silicoaluminate mesoporous molecularsieves leads to substantial increase of C3/C2 ratio, yield of lightolefins and stability in XTO than was obtained over the parent molecularsieve alone (MeAPO).

Higher stability of the blended catalysts together with the metal saltprovides a possibility to operate at higher flow rate, increase thecatalyst on-stream time in XTO conversion reactor and decrease the sizeof regeneration section or the frequency of regeneration. (on-streamtime is the time that a catalyst resides in the conversion reactor andexhibits still sufficient catalytic activity, before it has to be takenoff-line for regeneration or replacement)

Unexpectedly, this catalyst composite possesses reduced coke selectivityin comparison with the weighted average of the individual molecularsieves.

The excess of C4+ as well as ethylene can be converted to propylene inan olefin cracking fixed bed reactor (OCP) in combination with the XTOprocess. Ethylene can be recycled back in XTO reactor or to the OCPreactor. The excess C4+ as well as the ethylene can be converted to morepropylene by recycling C4+ and ethylene back to the XTO reactor. Thecatalyst blend allows the conversion of organic compounds, C4+ andethylene at the same time.

Stated above, small pore MeAPO molecular sieves contain 8-membered ringsas the largest pore aperture in the structure, medium pore crystallinesilicoaluminates contain 10-membered rings as the largest pore aperture;large pore crystalline silicoaluminates contain 12-membered rings as thelargest pore aperture. Stated above medium, large pore and mesoporousmolecular sieves have acidic properties, which are capable in catalysingthe formation of aromatic precursors from used feedstock.

In the XTO process the ethylene, propylene and higher hydrocarbons areformed via a “carbon pool” mechanism (Dahl and Kolboe 1994 Journal ofCatalysis 149(2): 458-464; Dahl and Kolboe 1996 Journal of Catalysis161(1): 304-309; Stocker 1999, Microporous and Mesoporous Materials29(1-2): 3-48). Ethylene, propylene and C4+ olefins selectivities in XTOprocess are related to the number of methyl groups attached to benzenerings trapped in the nanocages. The product spectrum varies stronglywith the pore size of the catalytic material (shape selectivity), andwhen the small pore SAPO-34 (chabasite structure) is used as catalystthe hydrocarbon products are mostly ethene and propene, and somesubstantially linear butenes, the only product molecules small enough toescape with ease through the narrow pores.

It has been discovered that medium or large pore crystallinesilicoaluminate, silicoaluminophosphate materials or silicoaluminatemesoporous molecular sieves play a role of a faster in-situ supply foraromatic precursors for olefin production by the carbon pool mechanism.One optional aspect of this invention is in-situ on-purpose formation ofsome additional organic reaction centers by adding to the MeAPO a smallamount of acid co-catalyst with larger pore opening than the MeAPO.These materials are capable to produce a small amount of highermolecular weight precursors that can enter into the pore system of thesmall pore MeAPO where they are converted into the aromatics under XTOconditions. These aromatics constitute the active centers for XTOaccording to the carbon pool mechanism. These aromatics are trapped byMeAPO micro porous system in a more optimum way without formation of alot of coke by-products. This allows an increased catalyst stability andC3/C2 ratio.

Without being bonded by any theory, inventors think that an optimumconcentration of the methylbenzenes organic reaction centers leads tohigher light olefins production and to a slower deactivation. Howeverthe olefin production is limited by diffusion of heavy olefins out ofthe micropore system of MeAPO in which usually methylbenzenes aretrapped. Formation of the methylbenzenes inside of MeAPO pore systemrequires a certain time and is accompanied by coke formation. More cokeformation in the small pore MeAPO reduces the accessible pore volume andresults in faster loss of catalytic activity.

BRIEF SUMMARY OF THE INVENTION

The invention covers a catalyst composite comprising:

-   -   at least 0.5% by weight of at least one metal salt stable under        XTO conditions and    -   at least 10% by weight of molecular sieve, which comprises:        -   70 to 100% by weight of at least one small pore            aluminosilicate or metalloaluminophosphate (MeAPO) molecular            sieve selected from the group CHA, AEI, ERI, LEV or a            mixture of thereof and        -   0 to 30% by weight of at least one medium or large pore            molecular sieve selected from one or more of crystalline            silicoaluminates, silicoaluminophosphates or mesoporous            silicoaluminates.

Preferably, the composite comprises from 0.5 to 10% by weight of atleast one metal salt, more preferably from 1 to 10%. The metal salt maycomprise at least one metal from the following: Zn, Co, Ca, Mg, Ga, Al,Cs, Sr, Ba, Sc, Sn and Li. Preferably, the metal is Zn, Co, Ca, Mg. Atleast one of the anions of the metal salt is advantageously selectedfrom silicates, borates and borosilicates.

Advantageously, the molecular sieves comprise 70 to 99.9% by weight ofthe MeAPO molecular sieve and 0.01 to 30% by weight of the medium orlarge pore molecular sieve. More advantageously, the molecular sievescomprise 75 to 99.5% by weight of the MeAPO molecular sieve and 0.5 to25% by weight of the medium or large pore molecular sieve. Mostadvantageously, the molecular sieves comprise 85 to 99% by weight of theMeAPO molecular sieve and 1 to 15% by weight of the medium or large poremolecular sieve.

MFI, FER and MEL are the most preferable medium pore crystallinesilicoaluminates.

AEL is the most preferable medium pore silicoaluminophosphate material.

FAU, MOR, LTL, MAZ, MWW and BEA are the most preferable large porecrystalline silicoaluminates.

AFI is the most preferable large pore silicoaluminophosphate materials,

MCM-41, SBA-15, SBA-16 are the most preferable mesoporous molecularsieve.

MeAPO's have a three-dimensional microporous crystal framework of PO₂ ⁺,AlO₂ ⁻, and MeO₂ tetrahedral units. MeAPO molecular sieves having CHA(SAPO-34, SAPO-44), LEV (SAPO-35), ERI (SAPO-17) or AEI (SAPO-18)structure or mixture thereof are the most preferable. Silicon is themost desirable metal in MeAPO.

According to another embodiment of the invention the MeAPO molecularsieve has an empirical chemical composition on an anhydrous basis, aftersynthesis and calcination, expressed by the formulaH_(x)Me_(y)Al₂P_(k)O₂ in which,

y+z+k=1

-   -   x<=y    -   y has a value ranging from 0.0008 to 0.4 and advantageously from        0.005 to 0.18    -   z has a value ranging from 0.25 to 0.67 and advantageously from        0.38 to 0.55    -   k has a value ranging from 0.2 to 0.67 and advantageously from        0.36 to 0.54

Advantageously said molecular sieve have predominantly plate crystalmorphology. Preferably said plate crystal morphology is such as thewidth (W) and the thickness (T) are as follows:

W/T is >=10 and advantageously ranges from 10 to 100.

According to another embodiment of the invention the MeAPO has beenprepared by a method comprising:

a) forming a reaction mixture containing a texture influencing agent(TIA), an organic templating agent (TEMP), at least a reactive inorganicsource of MeO₂ essentially insoluble in the TIA, reactive sources ofAl₂O₃ and P₂O₅,b) crystallizing the above reaction mixture thus formed until crystalsof the metalloaluminophosphate are formed,c) recovering a solid reaction product,d) washing it with water to remove the TIA ande) calcinating it to remove the organic template.

The catalyst composite can be obtained by introducing the metal salt tothe molecular sieve(s) by one of the following two methods:

-   -   During the formulation step of the catalyst by mechanically        blending the molecular sieve with the metal silicate forming a        precursor;    -   Physical blending of the previously formulated molecular sieve        and the previously formulated metal silicate in situ in the XTO        and/or OCP reaction medium.

The present invention also relates to a process (hereunder referred as“XTO process”) for making an olefin product from an oxygen-containing,halogenide-containing or sulphur-containing organic feedstock whereinsaid oxygen-containing, halogenide-containing or sulphur-containingorganic feedstock is contacted with the above catalyst composite (in theXTO reactor) under conditions effective to convert at least a portion ofthe oxygen-containing, halogenide-containing or sulphur-containingorganic feedstock to olefin products (the XTO reactor effluent). It isdesirable to have a substantially 100% conversion of the organiccompound in the XTO reactor. This conversion rate is adjusted byoptimization of the contact time and the frequency of regeneration ofthe catalyst composite.

According to a specific embodiment the XTO reactor effluent comprisinglight olefins and a heavy hydrocarbon fraction is sent to afractionation section to separate said light olefins from said heavyhydrocarbon fraction; said heavy hydrocarbon fraction is recycled in theXTO reactor at conditions effective to convert at least a portion ofsaid heavy hydrocarbon fraction to olefin products.

With regards to said effluent of the XTO process, “light olefins” meansethylene and propylene and the “heavy hydrocarbon fraction” is definedherein as the fraction containing hydrocarbons having a molecular weightgreater than propane, which means hydrocarbons having 4 carbon atoms ormore and written as C₄ ⁺.

According to another embodiment of the invention said olefin products(the effluent of the XTO) are fractionated to form a stream comprisingessentially ethylene and at least a part of said stream is recycled inthe XTO reactor to increase the propylene production and then theflexibility of ethylene vs propylene production.

According to another embodiment of the invention both ethylene and theC4+ can be recycled in the XTO reactor.

The present invention also relates to a process (hereunder referred as“combined XTO and OCP process”) to make light olefins from anoxygen-containing, halogenide-containing or sulphur-containing organicfeedstock comprising:

contacting said oxygen-containing, halogenide-containing orsulphur-containing organic feedstock in the XTO reactor with the abovecatalyst composite at conditions effective to convert at least a portionof the feedstock to form an XTO reactor effluent comprising lightolefins and a heavy hydrocarbon fraction;separating said light olefins from said heavy hydrocarbon fraction;contacting said heavy hydrocarbon fraction in the OCP reactor atconditions effective to convert at least a portion of said heavyhydrocarbon fraction to light olefins. It is desirable to have asubstantially 100% conversion of the organic compound in the XTOreactor. This conversion rate is adjusted by optimization of the contacttime and the frequency of regeneration of the catalyst.

DETAILED DESCRIPTION OF THE INVENTION

Regarding the small pore aluminosilicate and the small poremetalloaluminophosphate (MeAPO), they are known per se. MeAPO aredescribed in U.S. Pat. No. 4,440,871, U.S. Pat. No. 6,207,872, U.S. Pat.No. 6,540,970 and U.S. Pat. No. 6,303,534, the content of which areenclosed in the present application. Preferably they have essentiallythe structure SAPO-18 (AEI), SAPO-17(ERI), SAPO-35(LEV), SAPO-34 (CHA)or SAPO-44 (CHA) or a mixture thereof. In an advantageous embodiment theMeAPO molecular sieves have essentially a structure CHA or AEI or amixture thereof.

“Small pore” means typically having pore apertures defined by ring sizesof no more than 8 tetrahedric atoms, preferably ring sizes of 4, 6 or 8tetrahedric atoms. Preferably, the average pore size is less than about0.5 nm.

About “essentially” referring to the CHA or AEI structure it means thatadvantageously more than 80% by weight, preferably more than 90%, of theMeAPO has the structure CHA or AEI or a mixture thereof. About“essentially” referring to the SAPO-18, SAPO-34, SAPO-17, SAPO-35 andSAPO-44 structure, it means that advantageously more than 80% by weight,preferably more than 90%, of the MeAPO has the structure SAPO-18,SAPO-34, SAPO-44, SAPO-17, SAPO-35 or a mixture thereof.

Me is advantageously a metal selected from the group consisting ofsilicon, germanium, magnesium, zinc, iron, cobalt, nickel, manganese,chromium and mixtures thereof. Preferred metals are silicon, magnesiumand cobalt with silicon or germanium being especially preferred.

The MeAPO could be also an intergrown phase of two MeAPO having AEI andCHA framework types. They are described in U.S. Pat. No. 7,067,095, U.S.Pat. No. 6,953,767 and U.S. Pat. No. 6,334,994, the content of which areenclosed in the present application.

Before introduction of the metal salt promoter, other metals such as Si,Co, Zn, Ge, Mg, Ca, Ba, Ni, Mo, Cr, Cu, Fe, Ga, Mn, Sn, Ti may beintroduced.

Regarding the MeAPO according to another embodiment of the invention,the MeAPO molecular sieve has an empirical chemical composition on ananhydrous basis, after synthesis and calcination, expressed by theformula H_(x)Me_(y)Al_(z)P_(k)O₂ in which,

y+z+k=1

-   -   x<=y    -   y has a value ranging from 0.0008 to 0.4 and advantageously from        0.005 to 0.18    -   z has a value ranging from 0.25 to 0.67 and advantageously from        0.38 to 0.55    -   k has a value ranging from 0.2 to 0.67 and advantageously from        0.36 to 0.54

In an advantageous embodiment y has a value ranging from 0.005 to 0.18,z has a value ranging from 0.38 to 0.55 and k has a value ranging from0.36 to 0.54.

In a first preferred embodiment y has a value ranging from 0.005 to0.16, z has a value ranging from 0.39 to 0.55 and k has a value rangingfrom 0.37 to 0.54.

In a second preferred embodiment y has a value ranging from 0.011 to0.16, z has a value ranging from 0.39 to 0.55 and k has a value rangingfrom 0.37 to 0.54.

In a third preferred embodiment y has a value ranging from 0.011 to0.14, z has a value ranging from 0.40 to 0.55 and k has a value rangingfrom 0.38 to 0.54.

In an advantageous embodiment the MeAPO molecular sieves haveessentially a structure CHA or AEI or a mixture thereof. Preferably theyhave essentially the structure SAPO 18 or SAPO 34 or a mixture thereof.

Advantageously said molecular sieve have predominantly a plate crystalmorphology. Preferably said plate crystal morphology is such that thewidth (W) and the thickness (T) are as follows:

W/T is >=10 and advantageously ranges from 10 to 100.

In a preferred embodiment T is <=0.15 μm, more desirably <=0.10 μm, moredesirably <=0.08 μm, advantageously ranges from 0.01 to 0.07 μm andpreferably from 0.04 to 0.07 μm.

About the plate crystal morphology, said plates have advantageously theshape of a simple polygon comprised in a square. The square's length isnamed W. The MeAPO molecular sieves have predominantly a plate crystalmorphology. By predominantly is meant advantageously greater than 50% ofthe crystals. Preferably at least 70% of the crystals have a platemorphology and most preferably at least 90% of the crystals have a platemorphology. About “essentially” referring to the CHA or AEI structure itmeans that advantageously more than 80% by weight, preferably more than90%, of the MeAPO of the invention has the structure CHA or AEI or amixture thereof. About “essentially” referring to the SAPO-18, SAPO-34and SAPO-44 structure it means that advantageously more than 80% byweight, preferably more than 90%, of the MeAPO has the structure SAPO 18or SAPO 34 or a mixture thereof.

With regards to a method to make said MeAPO, it can be made by a methodwhich comprises:

a) forming a reaction mixture containing a texture influencing agent(TIA), an organic templating agent (TEMP), at least a reactive inorganicsource of MeO₂ essentially insoluble in the TIA, reactive sources ofAl₂O₃ and P₂O₅, said reaction mixture having a composition expressed interms of molar oxide ratios of:TEMP/Al₂O₃=0.3-5, more desirable 0.5-2MeO₂/Al₂O₃=0.005-2.0, more desirable 0.022-0.8P₂O₅/Al₂O₃=0.5-2, more desirable 0.8-1.2TIA/Al₂O₃=3-30, more desirable 6-20b) crystallizing the above reaction mixture thus formed until crystalsof the metalloaluminophosphate are formed,c) recovering a solid reaction product,d) washing it with water to remove the TIA ande) calcinating it to remove the organic template.

In an advantageous embodiment TEMP/Al₂O₃=0.5-2; MeO₂/Al₂O₃=0.022-0.8;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a first preferred embodiment TEMP/Al₂O₃=0.5-2; MeO₂/Al₂O₃=0.022-0.7;P₂O₅1Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a second preferred embodiment TEMP/Al₂O₃=0.7-2; MeO₂/Al₂O₃=0.05-0.7;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a third preferred embodiment TEMP/Al₂O₃=0.7-2; MeO₂/Al₂O₃=0.05-0.6;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

With regards to the TIA, mention may be made, by way of example, of1,2-propanediol, 1,3-propanediol, methanol, ethanol, propanol,isopropanol, butanol, glycerol or ethylene glycol.

With regards to the organic templating agent, it can be any of thoseheretofore proposed for use in the synthesis of conventional zeoliticaluminosilicates and microporous aluminophosphates. In general thesecompounds contain elements of Group VA of the Periodic Table ofElements, particularly nitrogen, phosphorus, arsenic and antimony,preferably N or P and most preferably N, which compounds also contain atleast one alkyl or aryl group having from 1 to 8 carbon atoms.Particularly preferred nitrogen-containing compounds for use astemplating agents are the amines and quaternary ammonium compounds, thelatter being represented generally by the formula R₄N⁺ wherein each R isan alkyl or aryl group containing from 1 to 8 carbon atoms. Polymericquaternary ammonium salts such as [(C₁₄H₃₂N₂)(OH)₂]_(x) wherein “x” hasa value of at least 2 are also suitably employed. Both mono-, di andtri-amines are advantageously utilized, either alone or in combinationwith a quaternary ammonium compound or other templating compound.Representative templating agents include tetramethylammonium,tetraethylammonium, tetrapropylammonium or tetrabutylammonium cations;di-n-propylamine, tripropylamine, triethylamine; diethylamine,triethanolamine; piperidine; morpholine; cyclohexylamine;2-methylpyridine; N,N-dimethylbenzylamine; N,N-diethylethanolamine;dicyclohexylamine; N,N-dimethylethanolamine; choline;N,N′-dimethylpiperazine; 1,4-diazabicyclo(2,2,2)octane;N-methyldiethanolamine, N-methylethanolamine; N-methylpiperidine;3-methylpiperidine; N-methylcyclohexylamine; 3-methylpyridine;4-methylpyridine; quinuclidine;N,N′-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine,neopentylamine; di-n-pentylamine; isopropylamine; t-butylamine;ethylenediamine; pyrrolidine; and 2-imidazolidone. Advantageouslyorganic templating agent is selected among tetraethylammonium hydroxide(TEAOH), diisopropylethylamine (DPEA), tetraethyl ammonium salts,cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine,diethylamine, cyclohexylamine, triethyl hydroxyethylamine, morpholine,dipropylamine, pyridine, isopropylamine di-n-propylamine,tetra-n-butylammonium hydroxide, diisopropylamine, di-n-propylamine,n-butylethylamine, di-n-butylamine, and di-n-pentylamine andcombinations thereof. Preferably the template, is a tetraethyl ammoniumcompound selected from the group of tetraethyl ammonium hydroxide(TEAOH), tetraethyl ammonium phosphate, tetraethyl ammonium fluoride,tetraethyl ammonium bromide, tetraethyl ammonium chloride, tetraethylammonium acetate. Most preferably, the template is tetraethyl ammoniumhydroxide.

With regards to the reactive inorganic source of MeO₂ essentiallyinsoluble in the TIA and relating to silicon, non-limiting examples ofuseful inorganic silicon source materials non-soluble in alcoholsinclude, fumed silica, aerosol, pyrogenic silica, precipitated silicaand silica gel.

With regards to the reactive sources of Al₂O₃, it can be any aluminumspecies capable of being dispersed or dissolved in an aqueous synthesissolution. Useful sources of alumina are one or more sources selectedfrom the group consisting of the following: hydrated alumina, organoalumina, in particularly Al(OiPr)₃, pseudo-boehmite, aluminum hydroxide,colloidal alumina, aluminium halides, aluminium carboxylates, aluminiumsulfates and mixtures thereof.

With regards to the reactive sources of P₂O₅, it can be one or moresources selected from the group consisting of phosphoric acid; organicphosphates, such as triethyl phosphate, tetraethyl-ammonium phosphate;aluminophosphates; and mixtures thereof. The phosphorous source shouldalso be capable of being dispersed or dissolved in an alcohol synthesissolution.

These MeAPO can be prepared by the usual methods of the molecular sievessynthesis technology provided it is in accordance with the above-citedratios. The reaction mixture is in the form of a gel. The ratiosMeO₂/Al₂O₃ and P₂O₅/Al₂O₃ are selected among the above describedadvantageous and preferred ratios and are in accordance with theadvantageous and preferred y, z and k described above. By way of exampleto make a MeAPO having the y, z and k according to the second preferredembodiment one has to use the ratios of the ingredients according to thesecond preferred embodiment of the method to make said MeAPO.

With regards to the step b), the reaction mixture obtained by mixing thereactive sources of alumina, MeO₂, phosphorus, organic templating agentand TIA is submitted to autogenous pressure and elevated temperature.The reaction mixture is heated up to the crystallization temperaturethat may range from about 120° C. to 250° C., preferably from 130° C. to225° C., most preferably from 150° C. to 200° C. Heating up to thecrystallization temperature is typically carried out for a period oftime ranging from about 0.5 to about 16 hours, preferably from about 1to 12 hours, most preferably from about 2 to 9 hours. The temperaturemay be increased stepwise or continuously. However, continuous heatingis preferred. The reaction mixture may be kept static or agitated bymeans of tumbling or stirring the reaction vessel during hydrothermaltreatment. Preferably, the reaction mixture is tumbled or stirred, mostpreferably stirred. The temperature is then maintained at thecrystallization temperature for a period of time ranging from 2 to 200hours. Heat and agitation is applied for a period of time effective toform crystalline product. In a specific embodiment, the reaction mixtureis kept at the crystallization temperature for a period of from 16 to 96hours.

With regards to the step c), the usual means can be used. Typically, thecrystalline molecular sieve product is formed as a slurry and can berecovered by standard means, such as by sedimentation, centrifugation orfiltration.

With regards to the step d), the separated molecular sieve product iswashed, recovered by sedimentation, centrifugation or filtration anddried.

With regards to the step e), calcination of molecular sieves is knownper se. As a result of the molecular sieve crystallization process, therecovered molecular sieve contains within its pores at least a portionof the template used. In a preferred embodiment, activation is performedin such a manner that the template is removed from the molecular sieve,leaving active catalytic sites with the microporous channels of themolecular sieve open for contact with a feedstock. The activationprocess is typically accomplished by calcining, or essentially heatingthe molecular sieve comprising the template at a temperature of from 200to 800° C. in the presence of an oxygen-containing gas. In some cases,it may be desirable to heat the molecular sieve in an environment havinga low oxygen concentration. This type of process can be used for partialor complete removal of the template from the intracrystalline poresystem.

Additionally, if during the synthesis alkaline or alkaline earth metalshave been used, the molecular sieve might be subjected to anion-exchange step. Conventionally, ion-exchange is done in aqueoussolutions using ammonium salts or inorganic acids.

Regarding the MeAPO according to another embodiment of the invention theMeAPO has been prepared by a method comprising:

a) forming a reaction mixture containing a texture influencing agent(TIA), an organic templating agent (TEMP), at least a reactive inorganicsource of MeO₂ essentially insoluble in the TIA, reactive sources ofAl₂O₃ and P₂O₅,b) crystallizing the above reaction mixture thus formed until crystalsof the metalloaluminophosphate are formed,c) recovering a solid reaction product,d) washing it with water to remove the TIA ande) calcinating it to remove the organic template.

In a usual embodiment said reaction mixture has a composition expressedin terms of molar oxide ratios of:

TEMP/Al₂O₃=0.3-5, more desirable 0.5-2MeO₂/Al₂O₃=0.005-2.0, more desirable 0.022-0.8P₂O₅/Al₂O₃=0.5-2, more desirable 0.8-1.2TIA/Al₂O₃=3-30, more desirable 6-20

In an advantageous embodiment TEMP/Al₂O₃=0.5-2; MeO₂/Al₂O₃=0.022-0.8;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a first preferred embodiment TEMP/Al₂O₃=0.5-2; MeO₂/Al₂O₃=0.022-0.7;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a second preferred embodiment TEMP/Al₂O₃=0.7-2; MeO₂/Al₂O₃=0.05-0.7;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a third preferred embodiment TEMP/Al₂O₃=0.7-2; MeO₂/Al₂O₃=0.05-0.6;P₂O₅/Al₂O₃=0.8-1.2 and TIA/Al₂O₃=6-20.

In a usual embodiment the metalloaluminophosphate (MeAPO) molecularsieves made with the above method have a lamellar crystal morphologyhaving an empirical chemical composition on an anhydrous basis, aftersynthesis and calcination, expressed by the formulaH_(x)Me_(y)Al_(z)P_(k)O₂ wherein,

y+z+k=1

x<=yy has a value ranging from 0.0008 to 0.4 and more desirable from 0.005to 0.18z has a value ranging from 0.25 to 0.67 and more desirable from 0.38 to0.55k has a value ranging from 0.2 to 0.67 and more desirable from 0.36 to0.54said molecular sieve having predominantly a plate crystal morphology.

The values of y, z and k in the usual embodiment are obtained by theratios of the ingredients described in the usual embodiment method abovedescribed.

In an advantageous embodiment y has a value ranging from 0.005 to 0.18,z has a value ranging from 0.38 to 0.55 and k has a value ranging from0.36 to 0.54.

In a first preferred embodiment y has a value ranging from 0.005 to0.16, z has a value ranging from 0.39 to 0.55 and k has a value rangingfrom 0.37 to 0.54.

In a second preferred embodiment y has a value ranging from 0.011 to0.16, z has a value ranging from 0.39 to 0.55 and k has a value rangingfrom 0.37 to 0.54.

In a third preferred embodiment y has a value ranging from 0.011 to0.14, z has a value ranging from 0.40 to 0.55 and k has a value rangingfrom 0.38 to 0.54.

The values of y, z and k in the advantageous, first, second and thirdembodiments described above are obtained by using the ingredients ratiosdescribed respectively in the advantageous, first, second and thirdembodiments of the method described above.

All the conditions already cited above relating to the synthesis of theMeAPO apply to said other embodiment of the invention.

The Catalyst Composite May Also Comprise One or More Medium or LargePore Molecular Sieves.

According to an embodiment of the invention, the catalyst composite maycomprise a mixture of MeAPO molecular sieves and medium or large porecrystalline silicoaluminates, silicoaluminophosphates or mesoporoussilicoaluminates. Among the products, which may be used for themolecular sieves of medium or large pore size, these include MFI, MEL,FER, MOR, FAU, BEA, AEL, AFI, LTL, MAZ, MWW and MCM-41. Preferably, theyhave pore apertures defined by ring sizes of 10 or more, preferably upto 12 tetrahedric atoms. More preferably, they have pore aperturesdefined by ring sizes of 10 or more, preferably up to 12 tetrahedricatoms and 10 or 12 oxygen atoms. Even more preferably, they have poresizes greater than 0.5 nm. Most preferably they are of the MFI (ZSM-5 orsilicalite), FAU, MOR, MEL or FER type. Zeolites may be pretreated byvarious ways, modified by P, by alkali, alkali-earth and/or rare-earthmetals. Pretreatment may be carried out by acid leaching, steaming orcombination thereof.

Advantageously (A) is a crystalline silicate of the MFI family which maybe a zeolite, a silicalite or any other silicate in that family or theMEL family which may be a zeolite or any other silicate in that family.Examples of MFI silicates are ZSM-5 and silicalite. An example of an MELzeolite is ZSM-11 which is known in the art. Other examples are BoraliteD and silicalite-2 as described by the International Zeolite Association(Atlas of Zeolite Structure Types, 1987, Butterworths). Preferably, themedium or large pore molecular sieve is one or more of ZSM-5, asilicalite, a ferrierite, a P-ZSM-5, a P-silicalite, or a P-ferrierite.

Crystalline silicates are microporous crystalline inorganic polymersbased on a framework of XO₄ tetrahydra linked to each other by sharingof oxygen ions, where X may be trivalent (e.g. Al, B, . . . ) ortetravalent (e.g. Ge, Si, . . . ). The crystal structure of acrystalline silicate is defined by the specific order in which a networkof tetrahedral units are linked together. The size of the crystallinesilicate pore openings is determined by the number of tetrahedral units,or, alternatively, oxygen atoms, required to form the pores and thenature of the cations that are present in the pores. They possess aunique combination of the following properties: high internal surfacearea; uniform pores with one or more discrete sizes; ionexchangeability; good thermal stability; and ability to adsorb organiccompounds. Since the pores of these crystalline silicates are similar insize to many organic molecules of practical interest, they control theingress and egress of reactants and products, resulting in particularselectivity in catalytic reactions. Crystalline silicates with the MFIstructure possess a bi-directional intersecting pore system with thefollowing pore diameters: a straight channel along [010]: 0.53-0.56 nmand a sinusoidal channel along [100]: 0.51-0.55 nm. Crystallinesilicates with the MEL structure possess a bi-directional intersectingstraight pore system with straight channels along [100] having porediameters of 0.53-0.54 nm.

The MFI or MEL catalyst having a high silicon/aluminum atomic ratio maybe manufactured by removing aluminum from a commercially availablecrystalline silicate. A typical commercially available silicalite has asilicon/aluminum atomic ratio of around 120 to 300. The commerciallyavailable MFI crystalline silicate may be modified by a steaming processwhich reduces the tetrahedral aluminum in the crystalline silicateframework and converts the aluminum atoms into octahedral aluminum inthe form of amorphous alumina. Although in the steaming step aluminumatoms are chemically removed from the crystalline silicate frameworkstructure to form alumina particles, those particles cause partialobstruction of the pores or channels in the framework. Accordingly,following the steaming step, the crystalline silicate is subjected to anextraction step wherein amorphous alumina is removed from the pores andthe micropore volume is, at least partially, recovered. The physicalremoval, by a leaching step, of the amorphous alumina from the pores bythe formation of a water-soluble aluminum complex yields the overalleffect of de-alumination of the MFI crystalline silicate. In this way byremoving aluminum from the MFI crystalline silicate framework and thenremoving alumina formed therefrom from the pores, the process aims atachieving a substantially homogeneous de-alumination throughout thewhole pore surfaces of the catalyst. This reduces the acidity of thecatalyst and thereby reduces the occurrence of hydrogen transferreactions in the cracking process. The framework silicon/aluminum ratiomay be increased by this process to a value of at least about 180,preferably from about 180 to 1000, more preferably at least 200, yetmore preferably at least 300 and most preferably around 480.

Regarding the mixture of the medium/large pore molecular sieve andMeAPO, if used, it can be made by co-synthesis procedure (synthesis ofMeAPO-(A) composites materials) optionally followed by formulation intoa catalyst. In another embodiment it can be formulated into a catalystby combining with other materials that provide additional hardness orcatalytic activity to the finished catalyst product. Materials, whichcan be blended with the mixture of medium/large pore molecular sieve andMeAPO can be various inert or catalytically active materials, or variousbinder materials. These materials include compositions such as kaolinand other clays, various forms of rare earth metals, alumina or aluminasol, titania, zirconia, quartz, silica or silica sol, and mixturesthereof. These components are effective in densifying the catalyst andincreasing the strength of the formulated catalyst. The catalyst may beformulated into pellets, spheres, extruded into other shapes, or formedinto a spray-dried powder.

The mixture of the medium/large pore molecular sieve and MeAPO can alsobe made by co-formulation procedure (blending of the separatelysynthesized medium/large pore molecular sieve and MeAPO) optionallyfollowed by combination with a binder. This mixture of medium/large poremolecular sieve and MeAPO can be used as itself as a catalyst. Inanother embodiment it can be formulated into a catalyst by combiningwith other materials that provide additional hardness or catalyticactivity to the finished catalyst product. The details are the same asabove.

The mixture of the medium/large pore molecular sieve and MeAPO can alsobe made by blending of MeAPO and the medium/large pore molecular sieve,wherein at least one of the two components has been combined with abinder prior to the blending. The obtained mixture can be used as itselfas a catalyst. In another embodiment it can be formulated into acatalyst by combining with other materials that provide additionalhardness or catalytic activity to the finished catalyst product. Thedetails are the same as above.

Preferably, the molecular sieves combination is a combination ofSAPO-34, SAPO-44 or SAPO-18 with a ZSM-5, a silicalite, a ferrierite ora P-ZSM-5, a P-silicalite, a P-ferrierite.

The presence of the medium and large pore molecular sieve is optional.Advantageously, the molecular sieves comprise 70 to 99.9% by weight ofthe MeAPO molecular sieve and 0.01 to 30% by weight of the medium orlarge pore molecular sieve. More advantageously, the molecular sievescomprise 75 to 99.5% by weight of the MeAPO molecular sieve and 0.5 to25% by weight of the medium or large pore molecular sieve. Mostadvantageously, the molecular sieves comprise 85 to 99% by weight of theMeAPO molecular sieve and 1 to 15% by weight of the medium or large poremolecular sieve.

According to an embodiment, the molecular sieves consist essentially ofthe MeAPO molecular sieve.

Regarding the metal salt, the catalyst composite further comprises atleast 0.5% by weight of a metal salt, which, advantageously, contains apolyvalent metal or a metal possessing a large hydration diameter. Morepreferably, the content of metal salt in the catalyst composite rangesfrom 0.5 up to 95% by weight of the composite, more preferably 5 to 80%by weight. Preferably, the metal in the metal salt is selected from Ga,Al, Cs, Sr, Mg, Ca, Ba, Sc, Sn, Li, Co, Zn, more preferably from amongZn, Co, Ca, Mg. Without wishing to be bound by theory, the ion exchangereaction with these ions is very slow. For example, calcium must losemany of the strongly coordinated water molecules in order to enter thestructure. Therefore, most of these ions cannot penetrate inside of themicropores and selectively poison the external surface. The specificityof the catalyst can thereby be better controlled.

The metal salt composition comprises at least one inorganic anionselected preferably from the group of silicates, borates andborosilicates. Suitable silicate anions include SiO₃ ²⁻, SiO₄ ⁴⁻, Si₂O₇⁶⁻ and so on. Suitable borate anions include BO₂ ⁻, BO₃ ²⁻, B₂O₅ ⁴⁻,B₄O₇ ²⁻, B₆O₁₁ ⁴⁻, B₁₀O₁₉ ⁸⁻ and so on.

Bi-, tri- and poly-metal silicates, borates and borosilicates containingone, two or more metals selected from the list above can be used too.

The metal salt may also comprise other anions besides silicate, boratesand borosilicates.

In an embodiment of the invention, a mixture of metal borates and metalsilicates can be used.

The metal salt according to the invention are stable under the XTOconditions of the reactor i.e. at a temperature of 200 to 700° C. and ata pressure of 5 kPa to 5 MPa, thus acting as a catalyst promoter.“Stable” refers to the fact that the elements constituting the metalsalt and having a positive valence remain part of the catalyst underpre-treatment conditions, XTO and regeneration conditions. This meansthat unlike metal oxides, the metal salts can be dehydrated, they maychange morphology and even change colour under the conditions of the XTOreactor, yet the inorganic anion would still be essentially present assuch. Furthermore, without wishing to be bound by theory, it is thoughtthat the presence of one or more of silicate, borate and borosilicateanions further improves the catalytic properties of the catalystcomposite.

Examples of suitable metal salt promoters include Mg₂B₂O₅.H₂O,CaMgB₆O₁₁.6H₂O (hydroboracite), Ca₂B₆O₁₁.5H₂O (colemanite),Ca₄B₁₀O₁₉.7H₂O, Mg(BO₂).8H₂O, Ca(BO₂).2H₂O, BaB₆O₁₀.4H₂O, CaSi₆O₁₇(OH)₂(Xonotlite), CaMg(Si₂O₆)_(x), Mg₂(Si₂O₆)_(x), CaAl₂Si₂O₈ and mixturesthereof.

The preferred catalyst promoter is a calcium silicate with a very openand accessible pore structure. An even more preferred catalyst promotercomprises a synthetic crystalline hydrated calcium silicate having achemical composition of Ca₆Si₆O₁₇(OH)₂ which corresponds to the knownmineral xonotlite (having a molecular formula 6CaO.6SiO₂.H₂O).

Generally, a synthetic hydrated calcium silicate is synthesisedhydrothermally under autogeneous pressure. A particularly preferredsynthetic hydrated calcium silicate is available in commerce from thecompany Promat of Ratingen in Germany under the trade name Promaxon.

In order to demonstrate the thermal stability of xonotlite, andtherefore the applicability of xonotlite as a catalyst promoter in MTOprocesses, commercial xonotlite sold under the trade name Promaxon D wascalcined in ambient air at a relative humidity of about 50% at 650° C.for a period of 24 hours. The initial xonotlite had a crystalline phaseCa₆Si₆O₁₇(OH)₂ with a BET surface area of 51 m²/gram and a pore volume(of less than 100 nanometres) of 0.35 ml/gram. After calcination at 650°C., the carrier retained its crystallinity, which corresponds to that ofxonotlite. Thus after a 24 hour calcination at 650° C., the crystallinephase still comprised xonotlite (Ca₆Si₆O₁₇(OH)₂) with a BET surface areaof 47.4 m²/gram and a pore volume (less than 100 nanometres) of 0.30ml/gram.

Before mixing with the molecular sieve said metal salt may be modifiedby calcination, steaming, ion-exchange, impregnation, or phosphatation.Said metal salt may be an individual compound or may be a part of mixedcompounds, for example mixed with mineral, natural or chemicalfertilizer.

The Metal Salt and Molecular Sieve(s) are Blended Together to Form theCatalyst Composite of the Invention.

The metal salt can be brought into contact with the molecular sieve by aco-formulation procedure or in situ blending in the reaction mediumprior to the XTO process. Said contact can be realised by mechanicallyblending the molecular sieves with the metal salt. This can be carriedout via any known blending method. Blending can last for a period oftime starting from 1 minute up to 24 hours, preferably from 1 min to 10hours. If not carried out in the XTO reactor in situ, it can be carriedout in a batchwise mixer or in a continuous process, such as in anextruder e.g. a single or twin screw extruder at a temperature of from20 to 300° C. under vacuum or elevated pressure. Said contact may beperformed in an aqueous or non-aqueous medium. Prior to the formulationstep, other compounds that aid the formulation may be added, likethickening agents or polyelectrolytes that improve the cohesion,dispersion and flowing properties of the precursor. In case ofextrusion, rotating granulation or pelletisng a rather dry (low watercontent) paste-like precursor is prepared. In case of oil-drop orspray-drying a rather liquid (high water content) is prepared. Inanother embodiment, the contact is carried out in the presence ofphosphorus containing compounds. In a particular embodiment, the contactis carried out in the aqueous medium, preferably at a pH lower than 5,more preferably lower than 3.

Either prior to, after or simultaneously with the formulation step toform the composite, other components may be optionally blended with themolecular sieve. In a particular embodiment, the molecular sieve can becombined with other materials that provide additional hardness orcatalytic activity to the finished catalyst product. Materials, whichcan be blended with the molecular sieve, can be various inert orcatalytically active matrix materials and/or various binder materials.Such materials include clays, silica and/or metal oxides such asalumina. The latter is either naturally occurring or in the form ofgelatinous precipitates or gels including mixtures of silica and metaloxides. In an embodiment, some binder materials can also serve asdiluents in order to control the rate of conversion from feed toproducts and consequently improve selectivity. According to oneembodiment, the binders also improve the crush strength of the catalystunder industrial operating conditions.

Naturally occurring clays, which can be used as binder, are for exampleclays from the kaolin family or montmorillonite family. Such clays canbe used in the raw state as mined or they can be subjected to varioustreatments before use, such as calcination, acid treatment or chemicalmodification.

In addition to the foregoing, other materials, which can be included inthe catalyst composite of the invention, include various forms of metalphosphates and sulphates (wherein the metal is chosen from one or moreof Ca, Ga, Al, Ca, Ce, In, Cs, Sr, Mg, Ba, Sc, Sn, Li, Zn, Co, Mo, Mn,Ni, Fe, Cu, Cr, Ti and V), alumina or alumina sol, titania, zirconia,quartz, silica or silica sol, and mixtures thereof. Examples of possiblephospates include amorphous calcium phosphate, monocalcium phosphate,dicalcium phosphate, dicalcium phosphate dehydrate, α- or β-tricalciumphosphate, octacalcium phosphate, hydroxyapatite etc.

Examples of possibly binary oxide binder compositions include,silica-alumina, silica magnesia, silica-zirconia, silica-thoria,silica-beryllia, silica-titania, calcium-alumina. Examples of ternarybinder compositions include for instance calcium-silica-alumina orsilica-alumina-zirconia.

These components are effective in increasing the density of the catalystand increasing the strength of the formulated catalyst. The catalyst maybe formulated into pellets, spheres, extruded into other shapes, orformed into spray-dried particles. Generally, the size of the catalystparticles can vary from about 20 to 5,000,000 μm. In general pellets,spheres and extrudates are employed in fixed bed reactors and exhibit aparticle size of from about 0.5 mm to 5 mm. In general spray-driedparticles are used in fluidised bed reactors, which exhibit a particlesize of from about 20 to 200 μm. In particular, spheres are employed inmoving bed reactors, which exhibit a size from about 0.5 to 5 mm.Spheres can be made in rotating granulator or by oil-drop methods. Thecrystal size of the molecular sieve contained in the catalyst compositeis preferably less than about 10 μm, more preferably less than about 5μm and most preferably less than about 4 μm. The amount of molecularsieve, which is contained in the final catalyst composite ranges from 10to 99.5% by weight of the total catalyst composite, preferably 20 to 80%by weight.

According to another embodiment, non-modified molecular sieves werefirst formulated with a binder and matrix materials and then modifiedwith phosphorous and alkaline earth metal silicates.

According to a further particular embodiment, molecular sieves wereoptionally dealuminated and then modified with phosphorous during theformulation step. Introduction of the alkaline earth metal silicate canbe performed during the formulation step or on the formulated solid.

According to a preferred embodiment, molecular sieves were firstoptionally dealuminated and modified with phosphorous and thenformulated. Introduction of the metal is performed simultaneously withthe phosphorous modification step and/or on the already formulatedcatalyst.

After physically blending the two components together, the catalystcomposite may undergo further treatments including further steaming,leaching, washing, drying, calcination, impregnations and ion exchangingsteps. If a zeolite is present, it can be modified with phosphorus priorto or after the step of introducing the metal salt to the molecularsieve.

With regards to the XTO process, the catalyst composite comprising themolecular sieves and metal salt according to the invention isparticularly suited for the catalytic conversion of oxygen-containing,halogenide-containing or sulphur-containing organic compounds tohydrocarbons. Accordingly, the present invention also relates to amethod for making an olefin product from an oxygen-containing,halogenide-containing or sulphur-containing organic feedstock whereinsaid oxygen-containing, halogenide-containing or sulphur-containingorganic feedstock is contacted with the above catalyst composite underconditions effective to convert the oxygen-containing,halogenide-containing or sulphur-containing organic feedstock to olefinproducts (the effluent of the XTO). Said effluent comprises lightolefins and a heavy hydrocarbon fraction.

In this process a feedstock containing an oxygen-containing,halogenide-containing or sulphur-containing organic compound contactsthe above described catalyst composite in a reaction zone of a reactorat conditions effective to produce light olefins, particularly ethyleneand propylene. Typically, the oxygen-containing, halogenide-containingor sulphur-containing organic feedstock is contacted with the catalystcomposite when the oxygen-containing, halogenide-containing orsulphur-containing organic compounds are in vapour phase. Alternately,the process may be carried out in a liquid or a mixed vapour/liquidphase. In this process, converting oxygen-containing,halogenide-containing or sulphur-containing organic compounds, olefinscan generally be produced at a wide range of temperatures. An effectiveoperating temperature range can be from about 200° C. to 700° C. At thelower end of the temperature range, the formation of the desired olefinproducts may become markedly slow. At the upper end of the temperaturerange, the process may not form an optimum amount of product. Anoperating temperature of at least 300° C., and up to 575° C. ispreferred.

The pressure also may vary over a wide range. Preferred pressures are inthe range of about 5 kPa to about 5 MPa, with the most preferred rangebeing of from about 50 kPa to about 0.5 MPa. The foregoing pressuresrefer to the partial pressure of the oxygen-containing,halogenide-containing, sulphur-containing organic compounds and/ormixtures thereof.

The process can be carried out in any system using a variety oftransport beds, although a fixed bed or moving bed system could be used.Advantageously a fluidized bed is used. It is particularly desirable tooperate the reaction process at high space velocities. The process canbe conducted in a single reaction zone or a number of reaction zonesarranged in series or in parallel. Any standard commercial scale reactorsystem can be used, for example fixed bed, fluidised or moving bedsystems. After a certain time on-stream the catalyst needs to beregenerated. This regeneration can be carried out in a separate reactoror in the same reactor. In case of a moving bed or fluidised bedreactor, a part of the catalyst is continuously or intermittentlywithdrawn from the conversion reactor and sent to a second reactor forregeneration. After the regeneration, the regenerated catalyst iscontinuously or intermittently sent back to the conversion reactor. Incase of fixed bed reactor the reactor is taken off-line forregeneration. Generally this requires a second spare reactor that cantake over the conversion into light olefins. After regeneration thefixed bed reactor is in stand-by until the spare reactor needsregeneration and the regenerated reactor takes over the conversion.Regeneration is carried out by injecting an oxygen-containing streamover the catalyst at sufficiently high temperature to burn the depositedcoke on the catalyst. The commercial scale reactor systems can beoperated at a weight hourly space velocity (WHSV) of from 0.1 hr⁻¹ to1000 hr⁻¹.

One or more inert diluents may be present in the feedstock, for example,in an amount of from 1 to 95 molar percent, based on the total number ofmoles of all feed and diluent components fed to the reaction zone.Typical diluents include, but are not necessarily limited to helium,argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water,paraffins, alkanes (especially methane, ethane, and propane), aromaticcompounds, and mixtures thereof. The preferred diluents are water andnitrogen. Water can be injected in either liquid or vapour form.

The oxygenate feedstock is any feedstock containing a molecule or anychemical having at least an oxygen atom and capable, in the presence ofthe above MeAPO catalyst composite, to be converted to olefin products.The oxygenate feedstock comprises at least one organic compound whichcontains at least one oxygen atom, such as aliphatic alcohols, ethers,carbonyl compounds (aldehydes, ketones, carboxylic acids, carbonates,esters and the like). Representative oxygenates include but are notnecessarily limited to lower straight and branched chain aliphaticalcohols and their unsaturated counterparts. Examples of suitableoxygenate compounds include, but are not limited to: methanol; ethanol;n-propanol; isopropanol; C₄-C₂₀ alcohols; methyl ethyl ether; dimethylether; diethyl ether; di-isopropyl ether; formaldehyde; dimethylcarbonate; dimethyl ketone; acetic acid; and mixtures thereof.Representative oxygenates include lower straight chain or branchedaliphatic alcohols, their unsaturated counterparts. Analogously to theseoxygenates, compounds containing sulphur or halides may be used.Examples of suitable compounds include methyl mercaptan; dimethylsulfide; ethyl mercaptan; di-ethyl sulfide; ethyl monochloride; methylmonochloride, methyl dichloride, n-alkyl halides, n-alkyl sulfideshaving n-alkyl groups of comprising the range of from about 1 to about10 carbon atoms; and mixtures thereof. Preferred oxygenate compounds aremethanol, dimethyl ether, or a mixture thereof.

In XTO effluent among the olefins having 4 carbon atoms or more thereare 50 to 85 weight % of butenes. More than 85% by weight andadvantageously more than 95% of the hydrocarbons having 4 carbon atomsor more are C4 to C8 olefins.

According to an advantageous embodiment of the invention said olefinproducts (the effluent of the XTO) are fractionated to form a streamcomprising essentially ethylene and at least a part of said stream isrecycled on the catalyst composite to increase the propylene productionand then the flexibility of ethylene vs propylene production.Advantageously the ratio of ethylene to the oxygen-containing,halogenide-containing or sulphur-containing organic feedstock is 1.8 orless.

The present invention also relates to a process (hereunder referred toas the “combined XTO and OCP process”) to make light olefins from anoxygen-containing, halogenide-containing or sulphur-containing organicfeedstock comprising:

contacting said oxygen-containing, halogenide-containing orsulphur-containing organic feedstock in the MTO reactor with the abovecatalyst at conditions effective to convert at least a portion of thefeedstock to form an MTO reactor effluent comprising light olefins and aheavy hydrocarbon fraction;separating said light olefins from said heavy hydrocarbon fraction;contacting said heavy hydrocarbon fraction in the OCP reactor atconditions effective to convert at least a portion of said heavyhydrocarbon fraction to light olefins.

The effluent of the XTO reactor comprising light olefins and a heavyhydrocarbon fraction is sent to a fractionation section to separate saidlight olefins from said heavy hydrocarbon fraction. With regards to saideffluent of the XTO process, “light olefins” means ethylene andpropylene and the “heavy hydrocarbon fraction” is defined herein as thefraction containing hydrocarbons having a molecular weight greater thanpropane, which means hydrocarbons having 4 carbon atoms or more andwritten as C₄ ⁺. It is desirable to have a substantially 100% conversionof the organic compound in the primary reactor. This conversion rate isadjusted by optimization of contact time and the frequency ofregeneration of the catalyst.

With regards to the OCP process, said process is known per se. It hasbeen described in EP 1036133, EP 1035915, EP 1036134, EP 1036135, EP1036136, EP 1036138, EP 1036137, EP 1036139, EP 1194502, EP 1190015, EP1194500 and EP 1363983 the content of which are incorporated in thepresent invention.

The heavy hydrocarbon fraction produced in the XTO reactor is convertedin the OCP reactor, also called an “olefin cracking reactor” herein, toproduce additional amounts of ethylene and propylene. Advantageously thecatalysts found to produce this conversion comprise a crystallinesilicate of the MFI family, which may be a zeolite, a silicalite or anyother silicate in that family, or of the MEL family, which may be azeolite or any other silicate in that family. These catalysts have beendescribed above in the description of the medium and large poremolecular sieves suitable for the invention.

The crystalline silicate catalyst has structural and chemical propertiesand is employed under particular reaction conditions whereby thecatalytic cracking of the C₄ ⁺ olefins readily proceeds. Differentreaction pathways can occur on the catalyst. Under the processconditions, having an inlet temperature of around 400° to 600° C.,preferably from 520° to 600° C., yet more preferably 540° to 580° C.,and an olefin partial pressure of from 0.1 to 2 bars, most preferablyaround atmospheric pressure. Olefinic catalytic cracking may beunderstood to comprise a process yielding shorter molecules via bondbreakage. With such high silicon/aluminum ratio in the crystallinesilicate catalyst, a stable olefin conversion can be achieved with ahigh propylene yield on an olefin basis.

The MFI catalyst having a high silicon/aluminum atomic ratio for use inthe OCP reactor of the present invention may be manufactured by removingaluminum from a commercially available crystalline silicate. A typicalcommercially available silicalite has a silicon/aluminum atomic ratio ofaround 120. The commercially available MFI crystalline silicate may bemodified by a steaming process, which reduces the tetrahedral aluminumin the crystalline silicate framework and converts the aluminum atomsinto octahedral aluminum in the form of amorphous alumina. Although inthe steaming step aluminum atoms are chemically removed from thecrystalline silicate framework structure to form alumina particles,those particles cause partial obstruction of the pores or channels inthe framework. This inhibits the olefin cracking processes of thepresent invention. Accordingly, following the steaming step, thecrystalline silicate is subjected to an extraction step whereinamorphous alumina is removed from the pores and the micropore volume is,at least partially, recovered. The physical removal, by a leaching step,of the amorphous alumina from the pores by the formation of awater-soluble aluminum complex yields the overall effect ofde-alumination of the MFI crystalline silicate. In this way by removingaluminum from the MFI crystalline silicate framework and then removingalumina formed there from the pores, the process aims at achieving asubstantially homogeneous de-alumination throughout the whole poresurfaces of the catalyst. This reduces the acidity of the catalyst andthereby reduces the occurrence of hydrogen transfer reactions in thecracking process. The reduction of acidity ideally occurs substantiallyhomogeneously throughout the pores defined in the crystalline silicateframework. This is because in the olefin-cracking process hydrocarbonspecies can enter deeply into the pores. Accordingly, the reduction ofacidity and thus the reduction in hydrogen transfer reactions whichwould reduce the stability of the MFI catalyst are pursued throughoutthe whole pore structure in the framework. The frameworksilicon/aluminum ratio may be increased by this process to a value of atleast about 180, preferably from about 180 to 1000, more preferably atleast 200, yet more preferably at least 300 and most preferably around480.

The MEL or MFI crystalline silicate catalyst may be mixed with a binder,preferably an inorganic binder, and shaped to a desired shape, e.g.extruded pellets. The binder is selected so as to be resistant to thetemperature and other conditions employed in the catalyst manufacturingprocess and in the subsequent catalytic cracking process for theolefins. The binder is an inorganic material selected from clays,silica, metal oxides such as ZrO₂ and/or metals, or gels includingmixtures of silica and metal oxides. The binder is preferablyalumina-free, although aluminum in certain chemical compounds as inaluminium phosphates (AlPO₄) may be used as the latter are quite inertand not acidic in nature. If the binder which is used in conjunctionwith the crystalline silicate is itself catalytically active, this mayalter the conversion and/or the selectivity of the catalyst. Inactivematerials for the binder may suitably serve as diluents to control theamount of conversion so that products can be obtained economically andorderly without employing other means for controlling the reaction rate.It is desirable to provide a catalyst having a good crush strength. Thisis because in commercial use, it is desirable to prevent the catalystfrom breaking down into powder-like materials. Such clay or oxidebinders have been employed normally only for the purpose of improvingthe crush strength of the catalyst. A particularly preferred binder forthe catalyst of the present invention comprises silica or AlPO₄.

The relative proportions of the finely divided crystalline silicatematerial and the inorganic oxide matrix of the binder can vary widely.Typically, the binder content ranges from 5 to 95% by weight, moretypically from 20 to 50% by weight, based on the weight of the compositecatalyst. Such a mixture of crystalline silicate and an inorganic oxidebinder is referred to as a formulated crystalline silicate.

In mixing the catalyst with a binder, the catalyst may be formulatedinto pellets, spheres, extruded into other shapes, or formed into aspray-dried powder. In the catalytic cracking process of the OCPreactor, the process conditions are selected in order to provide highselectivity towards propylene or ethylene, as desired, a stable olefinconversion over time, and a stable olefinic product distribution in theeffluent. Such objectives are favoured by the use of a low acid densityin the catalyst (i.e. a high Si/Al atomic ratio) in conjunction with alow pressure, a high inlet temperature and a short contact time, all ofwhich process parameters are interrelated and provide an overallcumulative effect. The process conditions are selected to disfavourhydrogen transfer reactions leading to the formation of paraffins,aromatics and coke precursors. The process operating conditions thusemploy a high space velocity, a low pressure and a high reactiontemperature. The LHSV ranges from 5 to 30 hr⁻¹, preferably from 10 to 30hr⁻¹. The olefin partial pressure ranges from 0.1 to 2 bars, preferablyfrom 0.5 to 1.5 bars (absolute pressures referred to herein). Aparticularly preferred olefin partial pressure is atmospheric pressure(i.e. 1 bar). The heavy hydrocarbon fraction feedstock is preferably fedat a total inlet pressure sufficient to convey the feedstocks throughthe reactor. Said feedstock may be fed undiluted or diluted in an inertgas, e.g. nitrogen or steam. Preferably, the total absolute pressure inthe second reactor ranges from 0.5 to 10 bars. The use of a low olefinpartial pressure, for example atmospheric pressure, tends to lower theincidence of hydrogen transfer reactions in the cracking process, whichin turn reduces the potential for coke formation, which tends to reducecatalyst stability. The cracking of the olefins is preferably performedat an inlet temperature of the feedstock of from 400° to 650° C., morepreferably from 450° to 600° C., yet more preferably from 540° C. to590° C., typically around 560° to 585° C.

In order to maximize the amount of ethylene and propylene and tominimize the production of methane, aromatics and coke, it is desired tominimize the presence of diolefins in the feed. Diolefin conversion tomonoolefin hydrocarbons may be accomplished with a conventionalselective hydrogenation process such as disclosed in U.S. Pat. No.4,695,560 hereby incorporated by reference.

The OCP reactor can be a fixed bed reactor, a moving bed reactor or afluidized bed reactor. A typical fluid bed reactor is one of the FCCtype used for fluidized-bed catalytic cracking in the oil refinery. Atypical moving bed reactor is of the continuous catalytic reformingtype. As described above, the process may be performed continuouslyusing a pair of parallel “swing” reactors. The heavy hydrocarbonfraction cracking process is endothermic; therefore, the reactor shouldbe adapted to supply heat as necessary to maintain a suitable reactiontemperature. Online or periodic regeneration of the catalyst may beprovided by any suitable means known in the art.

The various preferred catalysts of the OCP reactor have been found toexhibit high stability, in particular being capable of giving a stablepropylene yield over several days, e.g. up to ten days. This enables theolefin cracking process to be performed continuously in two parallel“swing” reactors wherein when one reactor is operating, the otherreactor is undergoing catalyst regeneration. The catalyst can beregenerated several times.

The OCP reactor effluent comprises methane, light olefins andhydrocarbons having 4 carbon atoms or more. Advantageously said OCPreactor effluent is sent to a fractionator and the light olefins arerecovered. Advantageously the hydrocarbons having 4 carbon atoms or moreare recycled at the inlet of the OCP reactor, optionally mixed with theheavy hydrocarbon recovered from the effluent of the XTO reactor.Advantageously, before recycling said hydrocarbons having 4 carbon atomsor more at the inlet of the OCP reactor, said hydrocarbons having 4carbon atoms or more are sent to a second fractionator to purge theheavies. In a preferred embodiment the light olefins recovered from theeffluent of the XTO reactor and the light olefins recovered from thefractionator following the OCP reactor are treated in a common recoverysection.

Optionally, in order to adjust the propylene to ethylene ratio of thewhole process (XTO+OCP), ethylene in whole or in part can be recycledover the OCP reactor and advantageously converted into more propylene.This ethylene can either come from the fractionation section of the XTOreactor or from the fractionation section of the OCP reactor or fromboth the fractionation section of the XTO reactor and the fractionsection of the OCP reactor or even from the optional common recoverysection.

Optionally, in order to adjust the propylene to ethylene ratio of thewhole process (XTO+OCP), ethylene in whole or in part can be recycledover the XTO reactor where it combines with the oxygen-containing,halogenide-containing or sulphur-containing organic feedstock to formmore propylene. This ethylene can either come from the fractionationsection of the XTO reactor or from the fractionation section of the OCPreactor or from both the fractionation section of the XTO reactor andthe fraction section of the OCP reactor or even from the optional commonrecovery section.

These ways of operation allow to respond with the same equipment andcatalyst to market propylene to ethylene demand.

The performance of the catalyst of the present invention issubstantially better than the simple sum of the individual components.This shows a synergy of at least one molecular sieve in the XTO and ametal salt to produce very particular catalytic properties. The catalystcomposite shows good behaviour in XTO processes in terms of stabilityand C3/C2 ratio, propylene purity and heavy olefins production (higherC4+ olefin yield for recycling).

FIG. 1 illustrates a specific embodiment of the invention. The effluentof the XTO reactor is passed to a fractionator 11. The overhead, a C1-C3fraction including the light olefins is sent via line 2 to a commonrecovery section (not shown). The bottoms (the heavy hydrocarbonfraction) are sent via line 3 to the OCP reactor. The effluent of theOCP reactor is sent via line 10 to a fractionator 8. The overhead, aC1-C3 fraction including the light olefins, is sent via line 9 to acommon recovery section (not shown). The bottoms, hydrocarbons having 4carbon atoms or more, are sent to a fractionator 5. The overhead,hydrocarbons having 4 to substantially 5 carbon atoms are recycled vialine 4 at the inlet of the OCP reactor. The bottoms, hydrocarbons havingsubstantially 6 carbon atoms or more, are purged via line 6.

The method of making the olefin products from an oxygenate feedstock caninclude the additional step of making the oxygenate feedstock fromhydrocarbons such as oil, coal, tar sand, shale, biomass and naturalgas. Methods for making oxygenate feedstocks are known in the art. Thesemethods include fermentation to alcohol or ether, making synthesis gas,then converting the synthesis gas to alcohol or ether. Synthesis gas canbe produced by known processes such as steam reforming, autothermalreforming and partial oxidization in case of gas feedstocks or byreforming or gasification using oxygen and steam in case of solid (coal,organic waste) or liquid feedstocks. Methanol, methylsulfide andmethylhalides can be produced by oxidation of methane with the help ofdioxygen, sulphur or halides in the corresponding oxygen-containing,halogenide-containing or sulphur-containing organic compound.

One skilled in the art will also appreciate that the olefin productsmade by the oxygenate-to-olefin conversion reaction using the molecularsieve of the present invention can be polymerized to form polyolefins,particularly polyethylenes and polypropylenes. The present inventionrelates also to said polyethylenes and polypropylenes.

EXAMPLES Example 1

A sample of SAPO-34 from UOP was obtained through “Customec”. Thissample showed a silicon content (Si/(Si+Al+P)) of 0.41 and represents acubic crystal morphology with an average size of 0.4 μm.

The sample is hereinafter identified as Comparative I.

Example 2

A sample identified hereinafter as Sample A was prepared by mechanicallyblending 80 wt % of the solid described in example I with 20 wt % ofxonotlite CaSi₆O₁₇(OH)₂.

Example 3

Catalyst tests were performed on 2 g catalyst samples with anessentially pure methanol feed at 450° C., at a pressure of 0.5 barg andWHSV=1.6 h⁻¹, in a fixed-bed, down-flow stainless-steel reactor.Catalyst powder was pressed into wafers and crushed to 35-45 meshparticles. Prior to catalytic run all catalysts were heated in flowingN₂ (5 NI/h) up to the reaction temperature. Analysis of the products hasbeen performed on-line by a gas chromatograph equipped with a capillarycolumn. Catalytic performances of MeAPOs molecular sieves were comparedat 100% methanol conversion and maximum catalyst activity just beforeappearance of DME in the effluent. The results are provided in Table I.The values regarding the composition of the effluent from the MTOreactor are the weight percent on a carbon basis and water-free.

TABLE I Comparative I Sample A SAPO-34 SAPO-34 + xonotlite 100 wt % 80wt % + 20 wt % T/° C. 450 450 WHSV/h⁻¹ 1.6 1.6 P/barg 0.5 0.5 C1 5.4 3.9Paraffins 8.4 5.8 Olefins 90.7 92.7 Aromatics 0.3 0.3 Purity C3's 97.899.4 C3/C2 0.7 0.7 C2 + C3 77.6 81.4 ethylene 44.8 46.7 propylene 32.734.7

1-41. (canceled)
 42. A catalyst composite comprising: at least 0.5% byweight of at least one metal salt, which is stable under temperatures of200 to 700° C. and pressures of 5 to 5000 kPa, wherein the metal saltcomprises a metal selected from a group consisting of Ga, Cs, Sr, Mg,Ca, Ba, Sc, Sn, Li, Co, Zn, and combinations thereof, and wherein themetal salt comprises an anion selected from a group consisting ofsilicates, borates, and borosilicates; at least 10% by weight ofmolecular sieves which comprise 70 to 100% by weight of molecular sievesof at least one small pore aluminosilicate or small poremetalloaluminophosphate (MeAPO) molecular sieve and 0 to 30% by weightof molecular sieves of at least one medium or large pore molecular sievecomprising pore apertures defined by ring sizes of at least 10tetrahedric atoms; wherein the at least one small pore aluminosilicateor small pore MeAPO molecular sieve comprises pore apertures defined byring sizes of up to 8 tetrahedric atoms; wherein the at least one mediumor large pore molecular sieve is selected from the group consisting ofcrystalline silicoaluminates, silicoaluminophosphates, mesoporoussilicoaluminates and combinations thereof.
 43. The catalyst composite ofclaim 42, wherein the metal is selected from a group consisting of Zn,Co, Ca, Mg, and combinations thereof.
 44. The catalyst composite ofclaim 42, wherein the metal is selected from a group consisting of Zn,Co, and combinations thereof.
 45. The catalyst composite of claim 42,wherein the metal is selected from a group consisting of Ca, Mg, andcombinations thereof.
 46. The catalyst composite of claim 42, whereinthe MeAPO molecular sieve has predominantly a plate crystal morphologyin which the width (W) and the thickness (T) are represented by theformula: W/T≧10.
 47. The catalyst composite of claim 46, wherein W/Tranges from 10 to
 100. 48. The catalyst composite of claim 46, wherein Tranges from 0.01 to 0.07 μm.
 49. The catalyst composite of claim 46,wherein T ranges from 0.04 to 0.07 μm.
 50. The catalyst composite ofclaim 42, wherein the catalyst composite comprises from 0.5% to 10% byweight of the at least one metal salt.
 51. The catalyst composite ofclaim 42, wherein the molecular sieves comprise 70 to 99.9% by weight ofthe MeAPO molecular sieve and 0.01 to 30% by weight of the medium orlarge pore molecular sieve.
 52. The catalyst composite of claim 42,wherein the molecular sieves comprise 75 to 99.5% by weight of the MeAPOmolecular sieve and 0.5 to 25% by weight of the medium or large poremolecular sieve.
 53. The catalyst composite of claim 42, wherein themedium pore crystalline silicoaluminate molecular sieves are selectedfrom a group consisting of MFI, FER, MEL and combinations thereof. 54.The catalyst composite of claim 42, wherein the medium pore crystallinesilicoaluminate molecular sieve is selected from a group consisting ofZSM-5, silicalite, P-ferrierite, and combinations thereof.
 55. Thecatalyst composite of claim 42, wherein the medium poresilicoaluminophosphate material is AEL.
 56. The catalyst composite ofclaim 42, wherein the large pore crystalline silicoaluminates areselected from a group consisting of FAU, MOR, LTL, MAZ, MWW, BEA, andcombinations thereof.
 57. The catalyst composite of claim 42, whereinthe large pore silicoaluminophosphate materials is AFI.
 58. The catalystcomposite of claim 42, wherein the mesoporous silicoaluminate is MCM-41.59. The catalyst composite of claim 42, wherein the MeAPO molecularsieves have essentially a structure CHA or AEI or a mixture thereof. 60.The catalyst composite of claim 42, wherein the MeAPO molecular sieveshave essentially the structure SAPO-18, SAPO-34, SAPO-44, SAPO-17,SAPO-35 or a mixture thereof.
 61. The catalyst composite of claim 42,wherein MeAPO is an intergrown phase of two MeAPO having AEI and CHAframework types.
 62. The catalyst composite of claim 42, wherein theMeAPO molecular sieve has an empirical chemical composition on ananhydrous basis, after synthesis and calcination, expressed by theformula H_(x)Me_(y)Al_(z)P_(k)O₂, in which:y+z+k=1; and x is less than or equal to y, wherein: y has a valueranging from 0.0008 to 0.4; z has a value ranging from 0.25 to 0.67; andk has a value ranging from 0.2 to 0.67.
 63. The catalyst composite ofclaim 42, wherein the MeAPO has been prepared by a method comprising:forming a reaction mixture containing a texture influencing agent (TIA),an organic templating agent (TEMP), and a reactive source wherein thereactive source is a reactive inorganic source of MeO₂ essentiallyinsoluble in the TIA, Al₂O₃, P₂O₅ or combinations thereof; crystallizingthe above reaction mixture thus formed until crystals of themetalloaluminophosphate (MeAPO) are formed; recovering a solid reactionproduct; washing it with water to remove the TIA; and calcinating it toremove the organic template.
 64. The catalyst composite of claim 42,wherein in the MeAPO, Me is a metal selected from a group consisting ofSi, Ge, Mg, Zn, Fe, Co, Ni, Mn, Cr, Ca, Ba, Mo, Cu, Ga, Sn, Ti, andmixtures thereof.
 65. The catalyst composite of claim 64, wherein Me isSi.
 66. The catalyst composite, of claim 42, wherein a metal selectedfrom a group consisting of Si, Mg, Zn, Ge, Fe, Co, Ni, Mn, Cr, Ca, Ba,Mo, Cu, Ga, Sn, Ti, and mixtures thereof is added to the molecularsieve(s) before blending with the metal salt.
 67. The catalyst compositeof claim 42, wherein the composite further comprises metal phosphatesand/or sulphates comprising at least one metal selected from a groupconsisting of Zn, Co, Ca, Mg, Ga, Al, Cs, Sr, Ba, Sc, Sn, and Li. 68.The catalyst composite of claim 42, wherein the metal salt is introducedto the molecular sieve(s) by one of the following two methods: duringthe formulation step of the catalyst by mechanically blending themolecular sieve with a metal silicate forming a precursor; or physicalblending of a previously formulated molecular sieve and a previouslyformulated metal silicate in situ in an XTO and/or OCP reaction medium.69. The catalyst composite of claim 68, wherein after introduction ofthe metal salt to the molecular sieve(s), the catalyst composite ispost-treated by calcination, reduction, steaming, or P-modification ofzeolites.
 70. A process for making an olefin product from anoxygen-containing, halogenide-containing or sulphur-containing organicfeedstock wherein the oxygen-containing, halogenide-containing orsulphur-containing organic feedstock is contacted in an XTO reactor withthe catalyst composite of claim 42 under conditions effective to convertthe oxygen-containing, halogenide-containing or sulphur-containingorganic feedstock to produce an XTO reactor effluent comprising a heavyhydrocarbon fraction and olefin products comprising ethylene andpropylene.
 71. The process of claim 70, wherein the XTO reactor effluentcomprising light olefins and a heavy hydrocarbon fraction is sent to afractionation section to separate said light olefins from the heavyhydrocarbon fraction and the heavy hydrocarbon fraction is recycled tothe XTO reactor at conditions in the XTO reactor effective to convert atleast a portion of the heavy hydrocarbon fraction to olefin products.72. The process of claim 71, wherein the olefin products arefractionated to form a stream comprised essentially of ethylene and atleast a part of said stream is recycled to the XTO reactor to increasethe propylene production.
 73. The process of claim 70, wherein the XTOreactor effluent comprising light olefins and a heavy hydrocarbonfraction is sent to a fractionation section to separate the lightolefins from said heavy hydrocarbon fraction and the heavy hydrocarbonfraction is sent in an OCP reactor at conditions in the OCP reactoreffective to convert at least a portion of the heavy hydrocarbonfraction to light olefins.
 74. The process of claim 73, wherein the OCPreactor effluent is sent to a fractionator and the light olefins arerecovered and hydrocarbons having 4 carbon atoms or more are recycled toan inlet of the OCP reactor, and mixed with the heavy hydrocarbonrecovered from the effluent of the XTO reactor.
 75. The process of claim74, wherein before recycling the hydrocarbons having 4 carbon atoms ormore to the inlet of the OCP reactor, the hydrocarbons having 4 carbonatoms or more are sent to a second fractionator to purge heavies. 76.The process of claim 75, wherein ethylene is recycled to the OCPreactor, and wherein the ethylene is from the fractionation section ofthe XTO reactor, from the fractionation section of the OCP reactor, fromboth the fractionation section of the XTO reactor and the fractionationsection of the OCP reactor, or from a common recovery section.
 77. Theprocess of claim 75, wherein ethylene is recycled to the XTO reactor,and wherein the ethylene is from the fractionation section of the XTOreactor, from the fractionation section of the OCP reactor, from boththe fractionation section of the XTO reactor and the fractionationsection of the OCP reactor, or from a common recovery section.
 78. Theprocess of claim 70, wherein the ethylene is polymerized with one ormore comonomers.
 79. The process of claim 70, wherein the propylene ispolymerized with one or more comonomers.